Cupriferous polyazo dyestuffs



Patented July 7, 1953 CUPRIFEROUS POLYAZO DYESTUFFS' Hans Ruckstuhl and Walter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel, switzerland, a Swiss firm No Drawing. Application January 16, 1952, Se-

rial No. 266,778. In Switzerland January 19,

The present invention relates to polyazo dyestuffs.

A primary object of the invention is the embodiment of a group, of polyazo dyestuffs characterized inter alia by superior afiinity for textile fibers, especially cotton and regenerated cellulose, and by their ability to yield dyeings in light-fast and wash-fast blue-gray to green-gray shades.

This object is realized, according to the present invention, by the cupriferous polyazo dyestuffs which are obtained when 1 mol of tetrazotized 3.3-dimethoxy-4,4 diamino 1,1 diphenyl is coupled first with 1 mol of the monoazo dyestufi (or of the copper complex thereof) of the formula wherein R stands for the radical, which is coupled in ortho-position to the hydroxy group thereof, of a hydroxynaphthalene or of a hydroxynaphthalene monosulfonic acid or of a hydroxynaphthalene disulfonic acid or of a hydroxynaphthalene trisulfonic acid or of a sulfonated pyrazolone or of an unsulfonated pyrazolone, and is then coupled with 1 mol of the same or any other coupling component, and the resultant polyazo dyestuff treated in substance or on the fiber with copper-yielding agents.

Illustrative R radicals in Formula 1, supra, are for example the radicals of:

As the second coupling component, there may 8 Claims. (Cl. 260,--145) f be used any of the precedingly-enumerated compounds, as Well as any other compound which couples in ortho-position to a phenolic hydroxy group or in ortho-position tea hydroxy group formed by enolization. Among others, the following compounds may be used in this regard:

2-amino-5-hydroxynaphthalene-7-sulfonic acid,

1 chlor0 2-amino-5-hydroxynaphthalene-7 sulfonic acid,

2 acetylamino-B-hydroxynaphthalene 7 sulionic acid,

2-benzoylamino-5-hydroxynaphthalene '7 fonic acid,

2 methylamino 5 hydroxynaphthalene-7-su1- fonic acid,

2 phenylamino-5-hydroxynaphthalene 7 sul fonic acid, 1-amino 8-hydroxynaphthalene-4-sulfonic acid, 1 phenylamino-8 hydroxynaphthalene 4 sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-(4'-carboxyphenylamino) -8-hydroxynaphtha lene-fi-sulfonic acid, 1-amino-8-hydroxynaphthalene 3,6 disulfonic acid; 1-acetylamino-8 -hydroxynaphthalene-Bfi-disulionic acid, 1-benzoylamino-8-hydroxynaphthalene 3,6 disulfonic acid, 1-amino-8-hydroxynaphthalene 2,4 disulfonic acid, l-amino-8-hydroxynaphthalene 3,5 disulfonic acid,

-Asu1- 2-amino-5-hydroxynaphthalene 1,7 disulfonic acid, 2-amino-B-hydroxynaphthalene 3,6- disulfonic 2-acetylamino-8-hydroxynaphthalene-3,6-disu1 fonic acid, 1,8 dihydroxynaphthalen'e 3,6 disulfonic acid,

etc.

It is to be understood that the preceding list is purely illustrative and is not at all intended to be limitative.

The monoazc dyestuffs used for coupling are preferably employed in the form of the copper complex, and they may be used for the first or for'the second. coupling with the tetrazotized 3,3-dimethoXy-4,4'-diamino1,1-diphenyl. The couplings are carried out in alkaline medium, preferably in medium made alkaline with sodium carbonate, although in some cases the second coupling may be carried out with the addition of pyridine.

To prepare the copper complex in substance, 250 parts of pyridine and 50 parts of aqueous the obtained corresponding polyazo dyestuff is ammonia, in 500 parts of water. Upon treated with copper-yielding agents until the completion of the coupling, the formed trisazo methoxy groups are split and the dyestufi has dyestuff is isolated and subjected to demethylatbeen converted into the copper complex. The 5 ing coppering. coppering' may be carried out in a diversity of The thus p'r'epared copper complex of the trisways which per se are known from the literature: azo dyestufi is, in the dry state, a dark powder for exampl y heating e dyesturf in weekly which dissolves in water with blue coloration and alkaline aqueous medium with copper tetramine in concentrated sulfuric acid with blue-green hydroxide complex in the presence or absence of 19 coloration, and dyes cotton in fast blue-gray an organic base or with the aid of fused alkali shades. metal salts of aliphatic monocaiboxylic acids It corresponds to the formula fi=N H038 H038 --ITI=N with copper salts. A dyestufi with similar-properties is obtained The products obtained according to the present in entirely analogous manner by replacing the invention dye cotton and regenerated cellulose in 55.2 parts of the copper complex of the monoaz'o blue-gray to green-gray shades. The dyeings are dyestufi of the Formula II, supra, by the correcharac't'erized by an outstanding affinity for the spending amount of the copper complex of the fiber, and the dyeings by very good fastness to monoazo dyestufi of the formula light and to washing.

It is also possible to dye the fabric with the uncoppered or partly coppered polyaao dyestuffs and then to treat the latter on the fiber with copper-yielding agents.

The renewing examples illustrate the invention by means of representative exemplary embodirnents thereof; these examples are 'ata-llto The thus-prepared product corresponds to the be considered as limitative of the scope of the formula o-cu-o 0 l l 1105s- --s'o n invention. The demethylating copper'in'g is in Example 2 each case per se conventional and may be carried I for example in the manner precedingly described. di 5 ggiififfig2ggi lfll ornhzig parts of 3 3 8 The isolation of the intermediate and of the final r a a P Y P roducts is carried out in each case in per se conm soda'alkahne medlum with 224 parts of p e I hydroxynaphthalene-4 sulfonic acid. The regllint f l l gaifl iz iifigfig f il sultant intermediate is isolated and introduced ter I into a solution of 63.2 partsof the copper complex of the monoazo dyestuif of the formula weight. The term soda refers to sodium carbonate.

Example 1 The tetrazo compound from 24.4 parts of 3,3- dimethoxy-QA-diamino-1,l'-diphenyl is coupled in soda alkalin'e medium with 30.4 parts of 1- hydroxynaphthalene-3,6-disulfonic acid. The 6 4 resultant intermediate is isolated and introduced 110 into a solution of 55.2 parts of the copper com- 250 parts of p r dme an to parts or aqueous plex or the monoazo dyestuff of the formula ammoma 5 0 parts of waterpon completlon f the pling, the formed t'risam H025 dyestufl isJiSOIatBd and subjected to deinethylating coppering.

The thus-prepared copper complex of the em. azo dyestufi is, in 'the dry state 'a dark powder which dissolves'in water aswell as in concentrated sulfuric acid with blue coloration, and dyes 'tton in fast b1ue=gray shades,

hoes -"so5H A dyestuif with similar properties is obtained in entirely analogous manner by replacing the 1-hydroxynaphthalene-4-sulfonic' acid by the 6 tion' and in concentrated sulfuric acid with bluish noas- 4on1 green coloration, and dyes cotton in greenish gray shades, V It corresponds to the formula corresponding amount of 2-hydroxynaphthalene- 4-sulfonic acid. The copper complex thus obtained corresponds to the formula Example 3 The tetrazo compound from 24.4 parts of 3,3'- dimethoXy-4,4'-diamino-1,1'-diphenyl is coupled in soda-alkaline medium with 32.0 parts of 1,8- dihydroxynaphthalene-3,6-disulfonic acid. The resultant intermediate is isolated and introduced into a solution of 58.2 parts of the copper complex of the monoazo dyestuif of the formula l a fl HO NC SO3H 250 parts of pyridine and 56 parts of aqueous ammonia (25%) in 500 parts of water. Upon completion of the coupling, the formed trisazo dyestuif is isolated and subjected to demethylating coppering.

The thus-prepared copper complex of the 65 dyes cotton in gray shades.

trisazo dyestuff is, in the dry state, a dark powder which dissolves in water with blue colora- The tetrazo compound from 24.4 parts or 3,3'-' dimethoxy-4,4'-diamino-1.l-diphenyl is subjected to soda-alkaline coupling with 63.2 parts of the copper complex of the monoazo dyestufl of the formula 5 (III) 0H l l in solution in 400 parts of water. The resultant fully-precipitated intermediate is filtered off and is introduced into a solution of 25.4 parts of 1- (4'-sulfophenyl)-3-methyl-5-pyrazolone and 40 parts of sodium carbonate in 500 parts of water. Upon completion of the coupling, the formed trisazo dyestuff is isolated and subjected to dec0 methylating coppering.

The thus prepared copper complex of the trisazo dyestuif is, in the dry state, a dark powder which dissolves in Water as well as in concentrated sulfuric acid with blue coloration, and

It corresponds to the formula 8 A dyestufl with similar properties is obtained phenyl)-3-methy1-5-pyra.zolone are replaced by in entirely analogous manner by replacing the an equivalent quantity of any one of the follow- 63.2 parts of the copper complex of the monoazo ing coupling components: dyestufi of Formula III, supra, by the corre- (a) 1 (2'-su1fopheny1)-3-methy1-5-pyrazo1one, spending quantity of the copper complex of the 5 (b) l (3'-su1fophenyl)-3-methy1-5-pyrazo1one, monoazo dyestuff of the formula, (0) 1 (3 earboxyphenyl) 3 methyl-S-pyrazolone,

OH (d) 1-pheny1-3-methy1-5-pyrazo1one,

HOSS (e) 1-pheny1-5-pyrazo1one-3-earboxy1ic acid,

10 (,f) 2 amino-5-hydroxynaphtha1ene-'7-su1fonie Ems -N=N acid I (a) 1-ch1oro-2-am1no-5-hydroxynephtha1ene-7- H H 03H sulfonic acid,

(h) 2 methylamino-S-hydroxynaphthe1ene-7- The thus-prepared product corresponds to the 15 sulfonic acid, or

formula. (1) 2 (4 carboxyphenylamino) 8 hydroxy- O-Cu-0 0 011-0 1 l nmsON-e i /C-N= 110,51 N=C J 110:8 N=N Ha i 0-611 0 0311 Furthermore, additional dyestufi's having simnaphthalene-fi-sulfmic acidilar properties are obtained if, while otherwise In each case, the Obtained final copper complex Proceeding as described in the first paragfaph of dyes cotton in fast gray shades. The formulae of t i pl the Parts Of 25 representative ones of these products follow:

| 0---( Ju-O o n-0 Q-s 1 1 I /CN=N H018 sod! N=C H 8 (BE: O ('?u Cu-0 o Cu-0 0- I s l 1 O-N=N N=N Ems -so,a

N==C H OOH O: 13I===N H: soda 0 Du-0 1-|I=N-N=N nois BO'H I -u t Hms- I H1C.HN 501K 0 eu-o l 15=NO -N=1 I 1101s 50.11 I i --Cu---O H038 I-=N o--eu-0 0 911-0 l l HOOC-O-HN -I I=N N=I I Hots SO:H

. 501E H015 1:I=N

9 0 Example 5 The tetrazo compound from 24.4 parts of 3,3- dimeth0xy-4A'-diamino-l,1'-diphenyl is added to a solution of 110.4 parts of thecopper complex of the monoazo dyestuff of the formula OH H0 500 parts of pyridine and 100 parts of aqueous ammonia (25 in 1000 parts of water. Upon completion of the coupling, the formed tetrakisazo dyestufi is isolated and subjected to de methylating coppering.

The thus prepared copper complex of the tetrakisazo dyestuff is, in the dry state, a dark 0 powder which dissolves in water with blue coloration and in concentrated sulfuric acid with greenblue coloration, and dyes cotton in greenish gray shades.

It corresponds to the formula SOIH Shade 0! g Copper Complex of- D eing on o. tton 6 H038 OH CHSO H OCH: OH blue-gray.

no ss03]: HOaS N=N H HO 7 H038 on 011, ?CHI 0H pay.

I CH3 noassou; I Hols- N=N-G- OH ll 0 s Hols on em com OH bluegray.

N=N N= soar: HO|SN- 9 OH 011. com on Do.

Example 22 7 on 20 parts or the dyestuff obtained according t Example 2 (first paragraph) are dissolved in 30,000 parts of water, and 300 parts of sodium 5 chloride are added. 1000 parts of cotton are added, the bath heated to boiling in the course of 30 (S0;N)--1 minutes, the bath maintained at the boil for 15 minutes and, after 15 additional minutes, the H0 1 material withdrawn, rinsed and. dried. The cotton is dyed a fast blue-gray shade. (50.11),

Having thus disclosed the invention, what is claimed is:

1. A copper complex compound of a polyazo dyestufi corresponding to the formula H0 N=Npyrazolone (s 0 3 n-i wherein R stands for the radical of a monoazo dyestuff selected from the group consisting of and N=N(i,'--C-l1 110-1: 1i on on E0: azo-naphtfralene 1 the OH group of naphthalene" and the nucleus and A respectively being linked to said radicals in 0 ortho-position to -azo-, n is one of the whole numbers 1, 2, 3 and 4, 111. being one of the whole -N= numbers 1, 2 and 3, x is a member selected from the group consisting of H, OH, --NH2, 1 -P NH-lower alkyl, NH-mononuclear aryl and (SOQHLH NH- acyl, y is a member selected from the OH group consisting of H, and Cl, 21 is a member I selected from the group consisting of CHa the OH group of naphthalene being linked and COOH, and 22 is a member selected from to said radical in ortho-position to -azo-, n is the group consisting of H and COOH. one of the whole numbers 1, 2, 3 and 4, and m is 2. A copper complex compound of a polyazo one of the whole numbers 1, 2 and 3, and wheredy st ff c sp nd g o e formula 0H moo 0cm on (sO3H)n-l N=N Orb on H018 azo-naphthalene H (OzHM-t in R stands for a substituent selected from the group consisting of wherein the OH group of "naphthalene is linked 0H thereto in ortho-position to -azo-, the OH group of nucleus A is linked thereto in ortho-position -N=N to N:N and m is one of the integers 1, 2

and 3. nos azo-naphtm 55 3. A copper complex compound of a polyazo (803mm dyestufi corresponding to the formula OH OH H i 0cm on l ..-1 N=C HO OH CH ale-naphthalene 

1. A COPPER COMPLEX COMPOUND OF A POLYAZO DYEDTUFF CORRESPONDING TO THE FORMULA 